The electro-Fenton (EF) process is a powerful electrochemical advanced oxidation process. Its development has progressed over the past three decades as a clean and effective technique for wastewater treatment. Even though conventional EF has been shown to be a powerful process for efficient degradation/mineralization of toxic and/or persistent organic pollutants; it still suffers from some downsides for industrial-scale development. Recently, research has focused on improving its effectiveness and relevance, mainly by modifying certain operating parameters; improvements in electrode material and reactor configuration, as well as coupling with other treatment methods. Therefore, this review evaluates the current state of the EF process and presents the most recent advances such as 3D-EF, chelate-EF, self-powered EF, pulsed current EF, bio-EF, sono-EF, sulfite-EF, pyrite-EF, and ferrate-EF in addition to its emerging applications like disinfection, generation of value-added products, and removal of emerging pollutants from water. The suitability of different modified or hybrid-EF processes is discussed based on their performance in H2O2 generation, degradation kinetics, mineralization efficiency and cost effectiveness. This review article is intended to be comprehensive, critical and of general interest, covering recent developments and advances in EF process with the aim of providing a powerful method for the treatment of wastewater polluted with biorecalcitrant pollutants.